metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Crystal structure of catena-poly[bis­(formato-κO)bis­­[μ2-1,1′-(1,4-phenyl­ene)bis­­(1H-imidazole)-κ2N3:N3′]cobalt(II)]

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aCollege of Science, China Three Gorges University, Yichang 443002, People's Republic of China, bCollege of Mechanical and Power Engineering, China Three Gorges University, YiChang 443002, People's Republic of China, and cCollege of Materials and Chemical Engineering, China Three Gorges University, YiChang 443002, People's Republic of China
*Correspondence e-mail: wzlsanxia@163.com

Edited by K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 18 July 2015; accepted 28 July 2015; online 6 August 2015)

A red block-shaped crystal of the title compound, [Co(HCOO)2(C12H10N4)2]n, was obtained by the reaction of cobalt(II) nitrate hexa­hydrate, formic acid and 1,1′-(1,4-phenyl­ene)bis­(1H-imidazole) (bib) mol­ecules. The asymmetric unit consists of one CoII cation, one formate ligand and two halves of a bib ligand. The central CoII cation, located on an inversion centre, is coordinated by two carboxyl­ate O atoms and four N atoms from bib ligands, completing an octa­hedral coordination geometry. The CoII centres are bridged by bib ligands, giving a two-dimensional net. Topologically, taking the CoII atoms as nodes and the bib ligands as linkers, the two-dimensional structure can be simplified as a typical sql/Shubnikov tetra­gonal plane network. The structure features C—H⋯O hydrogen-bonding inter­actions between formate and bib ligands, resulting in a three-dimensional supra­molecular network.

1. Related literature

For metal–organic framework structures, see: Yang et al. (2011[Yang, G.-S., Zang, H.-Y., Lan, Y.-Q., Wang, X.-L., Jiang, C.-J., Su, Z.-M. & Zhu, L.-D. (2011). CrystEngComm, 13, 1461-1466.], 2012[Yang, Q.-X., Chen, X.-Q., Cui, J., Hu, J., Zhang, M.-D., Qin, L., Wang, G.-F., Lu, Q.-Y. & Zheng, H.-G. (2012). Cryst. Growth Des. 12, 4072-4082.]); Guo & Sun (2012[Guo, M. & Sun, Z.-M. (2012). J. Mater. Chem. 22, 15939-15946.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [Co(CHO2)2(C12H10N4)2]

  • Mr = 569.44

  • Monoclinic, P 21 /c

  • a = 7.601 (6) Å

  • b = 11.715 (9) Å

  • c = 13.791 (10) Å

  • β = 99.017 (9)°

  • V = 1212.8 (16) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.76 mm−1

  • T = 293 K

  • 0.20 × 0.18 × 0.17 mm

2.2. Data collection

  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.732, Tmax = 1

  • 12595 measured reflections

  • 2773 independent reflections

  • 2059 reflections with I > 2σ(I)

  • Rint = 0.092

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.121

  • S = 1.07

  • 2773 reflections

  • 178 parameters

  • H-atom parameters constrained

  • Δρmax = 0.33 e Å−3

  • Δρmin = −0.41 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯O2i 0.93 2.40 3.330 (5) 173
C6—H6⋯O1i 0.93 2.49 3.383 (5) 161
C8—H8⋯O2ii 0.93 2.13 3.038 (5) 164
Symmetry codes: (i) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Many fantastic structures of metal-organic frameworks have been reported based on 1,4-bis­(1-imidazolyl)benzene. A lot of the them were constructed by mixed ligands including carboxyl­ate ligand, other N-donor molecule and wolframic acid or molybdic acid, see: Guo et al. (2012), Yang et al. (2011), Yang et al. (2012), Compared with those compounds constructed by mixed organic ligands, coordination polymers established by a single ligand, especially N-donor molecules, are much more useful and easier for understanding the theory of formation of supra­molecules. Accordingly, we selected 1,4-bis­(1-imidazolyl) benzene and cobalt(II), which always shows one or two coordinated ligands, to construct a new supra­molecule and study the structure of the title compound.

Synthesis and crystallization top

The title complex was synthesized by the reaction of 1,4-bis­(1-imidazolyl)benzene ( 10.5 mg, 0.05 mmol) in 8 ml of deionized water with cobalt(II) nitrate hexahydrate ( 29.1 mg, 0.1 mmol) in 20ml of methanol and the mixture was refluxed for 1 hour. To the above mixture, 0.5 ml of formic acid was added and the result fluid was placed in a Teflon-lined, stainless-steel reactor. The reactor was heated to 413 K for 96 hours. It was then cooled to room temperature. Red block crystals were isolated in 69% yield (based on bib ligand).

Refinement details top

All the hydrogen atoms in the molecule were identified from the difference electron density map, further idealized and treated as riding with a distance d(C—H)=0.93Å In all cases Uiso(H)=-1.2Ueq.

Related literature top

For metal–organic framework structures, see: Yang et al. (2011, 2012); Guo & Sun (2012).

Structure description top

Many fantastic structures of metal-organic frameworks have been reported based on 1,4-bis­(1-imidazolyl)benzene. A lot of the them were constructed by mixed ligands including carboxyl­ate ligand, other N-donor molecule and wolframic acid or molybdic acid, see: Guo et al. (2012), Yang et al. (2011), Yang et al. (2012), Compared with those compounds constructed by mixed organic ligands, coordination polymers established by a single ligand, especially N-donor molecules, are much more useful and easier for understanding the theory of formation of supra­molecules. Accordingly, we selected 1,4-bis­(1-imidazolyl) benzene and cobalt(II), which always shows one or two coordinated ligands, to construct a new supra­molecule and study the structure of the title compound.

For metal–organic framework structures, see: Yang et al. (2011, 2012); Guo & Sun (2012).

Synthesis and crystallization top

The title complex was synthesized by the reaction of 1,4-bis­(1-imidazolyl)benzene ( 10.5 mg, 0.05 mmol) in 8 ml of deionized water with cobalt(II) nitrate hexahydrate ( 29.1 mg, 0.1 mmol) in 20ml of methanol and the mixture was refluxed for 1 hour. To the above mixture, 0.5 ml of formic acid was added and the result fluid was placed in a Teflon-lined, stainless-steel reactor. The reactor was heated to 413 K for 96 hours. It was then cooled to room temperature. Red block crystals were isolated in 69% yield (based on bib ligand).

Refinement details top

All the hydrogen atoms in the molecule were identified from the difference electron density map, further idealized and treated as riding with a distance d(C—H)=0.93Å In all cases Uiso(H)=-1.2Ueq.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A part of the crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level, The H atoms have been removed for clarity. Symmetry codes: (A) -x, 2 - y, 1 - z; (B) 1 - x, 1 - y, -z.
catena-Poly[bis(formato-κO)bis[µ2-1,1'-(1,4-phenylene)bis(1H-imidazole)-κ2N3:N3']cobalt(II)] top
Crystal data top
[Co(CHO2)2(C12H10N4)2]F(000) = 586
Mr = 569.44Dx = 1.559 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.601 (6) ÅCell parameters from 2599 reflections
b = 11.715 (9) Åθ = 2.3–27.5°
c = 13.791 (10) ŵ = 0.76 mm1
β = 99.017 (9)°T = 293 K
V = 1212.8 (16) Å3Block, red
Z = 20.20 × 0.18 × 0.17 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
2059 reflections with I > 2σ(I)
Detector resolution: 13.6612 pixels mm-1Rint = 0.092
φ and ω scansθmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 99
Tmin = 0.732, Tmax = 1k = 1515
12595 measured reflectionsl = 1717
2773 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.121 w = 1/[σ2(Fo2) + (0.0395P)2 + 0.7123P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2773 reflectionsΔρmax = 0.33 e Å3
178 parametersΔρmin = 0.41 e Å3
Crystal data top
[Co(CHO2)2(C12H10N4)2]V = 1212.8 (16) Å3
Mr = 569.44Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.601 (6) ŵ = 0.76 mm1
b = 11.715 (9) ÅT = 293 K
c = 13.791 (10) Å0.20 × 0.18 × 0.17 mm
β = 99.017 (9)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
2773 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
2059 reflections with I > 2σ(I)
Tmin = 0.732, Tmax = 1Rint = 0.092
12595 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.07Δρmax = 0.33 e Å3
2773 reflectionsΔρmin = 0.41 e Å3
178 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.00001.00000.00000.02562 (17)
O10.1750 (3)1.11742 (17)0.07673 (16)0.0356 (5)
N40.3551 (3)0.7072 (2)0.0552 (2)0.0357 (6)
N20.0995 (4)0.9605 (2)0.29716 (18)0.0327 (6)
N30.1856 (4)0.8626 (2)0.04773 (19)0.0340 (6)
C40.0494 (4)0.9811 (2)0.4001 (2)0.0294 (6)
N10.1089 (4)0.9758 (2)0.13562 (18)0.0340 (6)
C60.0753 (4)0.8960 (3)0.4668 (2)0.0330 (7)
H60.12520.82650.44460.040*
C110.4328 (5)0.5795 (3)0.0706 (3)0.0452 (9)
H110.38790.63240.11840.054*
C50.0263 (4)1.0845 (3)0.4333 (2)0.0336 (7)
H50.04421.14100.38850.040*
C10.2136 (5)0.8854 (3)0.1559 (2)0.0454 (9)
H10.27800.83860.10870.055*
C100.4314 (4)0.6030 (3)0.0271 (2)0.0361 (7)
C20.2098 (5)0.8742 (3)0.2544 (2)0.0459 (9)
H20.26890.81980.28640.055*
C90.2525 (4)0.7840 (2)0.0035 (2)0.0343 (7)
H90.23260.78080.07170.041*
C30.0435 (4)1.0190 (3)0.2222 (2)0.0346 (7)
H30.03181.08200.23100.041*
C130.3415 (5)1.1113 (3)0.0969 (2)0.0422 (8)
H130.39481.05180.06750.051*
O20.4414 (4)1.1735 (3)0.1501 (2)0.0710 (9)
C120.4980 (5)0.5242 (3)0.0977 (3)0.0448 (9)
H120.49690.54020.16360.054*
C70.2476 (5)0.8367 (3)0.1452 (3)0.0527 (10)
H70.22200.87850.19860.063*
C80.3512 (5)0.7414 (3)0.1518 (3)0.0494 (10)
H80.40760.70640.20880.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0335 (3)0.0221 (3)0.0210 (3)0.0044 (2)0.0034 (2)0.0006 (2)
O10.0393 (13)0.0303 (11)0.0360 (12)0.0005 (10)0.0022 (10)0.0054 (10)
N40.0356 (15)0.0274 (13)0.0432 (16)0.0054 (11)0.0030 (12)0.0014 (12)
N20.0405 (15)0.0345 (13)0.0238 (13)0.0026 (11)0.0080 (11)0.0009 (11)
N30.0392 (15)0.0287 (13)0.0324 (14)0.0093 (11)0.0006 (11)0.0020 (11)
C40.0326 (16)0.0344 (16)0.0215 (13)0.0027 (13)0.0057 (12)0.0011 (12)
N10.0426 (15)0.0347 (14)0.0254 (12)0.0002 (11)0.0082 (11)0.0004 (11)
C60.0431 (18)0.0277 (15)0.0283 (15)0.0018 (13)0.0062 (14)0.0029 (13)
C110.054 (2)0.0387 (18)0.043 (2)0.0143 (17)0.0071 (17)0.0073 (16)
C50.0444 (19)0.0303 (16)0.0268 (15)0.0013 (14)0.0080 (14)0.0061 (13)
C10.052 (2)0.058 (2)0.0268 (16)0.0157 (18)0.0059 (15)0.0035 (16)
C100.0327 (17)0.0296 (16)0.0461 (19)0.0053 (13)0.0063 (14)0.0000 (14)
C20.058 (2)0.051 (2)0.0287 (17)0.0178 (18)0.0064 (16)0.0003 (16)
C90.0393 (18)0.0290 (15)0.0343 (17)0.0070 (14)0.0046 (14)0.0017 (13)
C30.0447 (19)0.0346 (17)0.0258 (15)0.0006 (14)0.0100 (13)0.0012 (13)
C130.045 (2)0.0397 (19)0.0398 (19)0.0021 (16)0.0017 (16)0.0043 (15)
O20.0624 (19)0.078 (2)0.0664 (19)0.0092 (16)0.0096 (15)0.0266 (17)
C120.057 (2)0.0379 (18)0.0400 (18)0.0143 (16)0.0079 (17)0.0024 (15)
C70.064 (3)0.047 (2)0.043 (2)0.0232 (19)0.0058 (18)0.0095 (17)
C80.063 (3)0.043 (2)0.0364 (19)0.0180 (18)0.0110 (17)0.0037 (16)
Geometric parameters (Å, º) top
Co1—O1i2.083 (2)N3—C71.387 (4)
Co1—O12.083 (2)C4—C51.387 (4)
Co1—N3i2.173 (3)C4—C61.391 (4)
Co1—N32.173 (3)N1—C31.320 (4)
Co1—N12.179 (3)N1—C11.379 (4)
Co1—N1i2.179 (3)C6—C5ii1.389 (4)
O1—C131.254 (4)C11—C101.377 (5)
N4—C91.369 (4)C11—C12iii1.397 (4)
N4—C81.396 (4)C5—C6ii1.389 (4)
N4—C101.431 (4)C1—C21.361 (5)
N2—C31.363 (4)C10—C121.379 (4)
N2—C21.385 (4)C13—O21.212 (4)
N2—C41.432 (4)C12—C11iii1.397 (4)
N3—C91.311 (4)C7—C81.360 (5)
O1i—Co1—O1180.0C9—N3—Co1130.2 (2)
O1i—Co1—N3i90.15 (11)C7—N3—Co1124.2 (2)
O1—Co1—N3i89.84 (11)C5—C4—C6120.1 (3)
O1i—Co1—N389.85 (11)C5—C4—N2120.4 (3)
O1—Co1—N390.16 (11)C6—C4—N2119.5 (3)
N3i—Co1—N3180.00 (13)C3—N1—C1105.0 (3)
O1i—Co1—N192.97 (10)C3—N1—Co1125.9 (2)
O1—Co1—N187.03 (10)C1—N1—Co1125.6 (2)
N3i—Co1—N192.33 (10)C5ii—C6—C4119.6 (3)
N3—Co1—N187.67 (10)C10—C11—C12iii119.7 (3)
O1i—Co1—N1i87.04 (10)C4—C5—C6ii120.2 (3)
O1—Co1—N1i92.96 (10)C2—C1—N1110.7 (3)
N3i—Co1—N1i87.67 (10)C11—C10—C12119.9 (3)
N3—Co1—N1i92.33 (10)C11—C10—N4120.1 (3)
N1—Co1—N1i180.0C12—C10—N4119.9 (3)
C13—O1—Co1128.1 (2)C1—C2—N2105.7 (3)
C9—N4—C8106.2 (3)N3—C9—N4112.1 (3)
C9—N4—C10128.2 (3)N1—C3—N2112.0 (3)
C8—N4—C10125.0 (3)O2—C13—O1127.9 (4)
C3—N2—C2106.5 (3)C10—C12—C11iii120.3 (3)
C3—N2—C4127.0 (3)C8—C7—N3110.4 (3)
C2—N2—C4126.5 (3)C7—C8—N4105.8 (3)
C9—N3—C7105.5 (3)
Symmetry codes: (i) x, y+2, z; (ii) x, y+2, z+1; (iii) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2iv0.932.403.330 (5)173
C3—H3···O10.932.573.026 (4)111
C6—H6···O1iv0.932.493.383 (5)161
C8—H8···O2v0.932.133.038 (5)164
Symmetry codes: (iv) x, y1/2, z+1/2; (v) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.403.330 (5)173
C3—H3···O10.932.573.026 (4)111
C6—H6···O1i0.932.493.383 (5)161
C8—H8···O2ii0.932.133.038 (5)164
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
 

Acknowledgements

This work was supported financially by the Graduate Student Research Innovation Fund of CTGU (CX2014094) and the Training Excellent Masters Thesis Fund of CTGU (Nos. PY2015074 and PY2015030), China.

References

First citationBruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGuo, M. & Sun, Z.-M. (2012). J. Mater. Chem. 22, 15939–15946.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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